CN101995588B - Method for producing optical article - Google Patents
Method for producing optical article Download PDFInfo
- Publication number
- CN101995588B CN101995588B CN201010250256.XA CN201010250256A CN101995588B CN 101995588 B CN101995588 B CN 101995588B CN 201010250256 A CN201010250256 A CN 201010250256A CN 101995588 B CN101995588 B CN 101995588B
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- China
- Prior art keywords
- layer
- optical article
- niobium
- titanium
- ground floor
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
- G02B1/116—Multilayers including electrically conducting layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00865—Applying coatings; tinting; colouring
-
- G02B1/105—
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/121—Antistatic or EM shielding layer
Abstract
The invention provides a method for producing an optical article capable of forming a layer with excellent electrical prevention performance. The invention provides the method for producing the optical article, comprising the following steps of: forming a light-transmissive first layer on an optical substrate, either directly or with another layer in between; and depositing, by ion-assisted deposition, a composition comprising at least one of titanium, niobium, an oxide of titanium and an oxide of niobium onto at least a portion of the surface layer of the first layer in order to reduce the resistance of the surface layer. Although the optical article is titanium-niobium, the optical article can reduce the resistance at the surface without high-temperature treatment, thereby reducing the resistance without using expensive indium.
Description
Technical field
The present invention relates to the manufacture method of the optical article using in the eyeglasses such as eyeglass, other optical materials or goods.
Background technology
The optical articles such as eyeglass, on the surface of the base material for bringing into play various functions (optical element), are formed with the layer (film) with various functions further to strengthen or to protect the function of this base material.For example, be known to the hard conating of the permanance for guaranteeing eyeglass base material, for preventing antireflection layer of ghost image and flash of light etc.The exemplary of antireflection layer is so-called reflection multilayer preventing layer, and it is to have the surface oxide film that alternately lamination has a different refractivity of the eyeglass base material of hard conating to form in lamination.
In patent documentation 1, record following content: provide a kind of novel charged optical element that prevents function of having of low heat resistant base material that is suitable for.Record the optical elements such as a kind of eyeglass, it has the antireflection film of sandwich construction on plastic optical element, wherein, antireflection film comprises transparency conducting layer, this transparency conducting layer forms by ion assisted vacuum evaporation, and the constituting layer of other antireflection layers is by formation such as electron beam vacuum evaporations.Record as conductive layer and can enumerate using any one or the two or more inorganic oxide as composition in indium, tin, zinc etc., especially wish it is ITO (Indium Tin Oxide: the potpourri of indium oxide and tin oxide).
[patent documentation 1] TOHKEMY 2004-341052 communique
No. 2006/016608 book of [patent documentation 2] International Publication
[patent documentation 3] TOHKEMY 2004-300580 communique
In the field of the optical articles such as eyeglass, in order to prevent charged and shielding electromagnetism etc., seek to replace the method that uses the ITO of expensive indium and form the layer that electric conductivity can be provided.One of this method is the titanium niobium oxide (Ti that is called TNO
1-Xnb
xo
2).In patent documentation 2, record about transparency electrode base material transparent and that there is electric conductivity and transparent conducting film, provide can stable supplying and formed by the material of the excellences such as chemical resistance transparent metal material and transparency electrode.In addition, record following content: by form the metal oxide layer being formed by sharp titanium (anatase) type crystal structure on substrate, utilize TiO
2form metal oxide layer, in maintaining internal transmission rate, realize low-resistivity thus, that is, manufacture and utilize other atoms (Nb, Ta, Mo, As, Sb, W etc.) displacement anatase titanium dioxide TiO
2in Ti lattice point and the TiO that obtains
2, can maintain thus transparency and significantly improve conductivity.
But the substrate temperature need to be by this transparent metal of evaporation time maintains under 550 DEG C of such high temperature.This pyroprocessing, for obtaining the crystal structure of anatase titanium dioxide, need to remain on 300 DEG C of above processing in order to generate TNO film.On the other hand, the heat resisting temperature of glass lens is the highest also with regard to 100 DEG C.Therefore, can not adopt and follow the TNO of pyroprocessing to substitute the conductive layer of ITO as glass lens.
For example, in patent documentation 3, record following content: provide following evaporation composition manufacture method, there is the manufacture method of the optics of evaporation composition and antireflection film, even evaporation also can form high refractive index layer under cryogenic conditions, can obtain wearing quality, chemical resistance and thermotolerance good and along with the less antireflection film of degree of process the thermotolerance reduction of time.In addition, also record manufacture method, the evaporation composition of evaporation composition and there is the manufacture method of the optical article of antireflection film, the manufacture method of evaporation composition is characterised in that, the evaporation raw mixture that sintering is obtained by mixing the evaporation raw material that contains titania and niobium pentoxide; Evaporation composition is characterised in that, this evaporation composition contains titania and niobium pentoxide; The manufacture method with the optical article of antireflection film is characterised in that, produces the steam of this evaporation composition, and the evaporant producing is separated out on substrate, forms the high refractive index layer of antireflection film.There is high index of refraction although contain evaporation forms under cryogenic conditions titania and the evaporation composition of niobium pentoxide, be not conceived to resistance, in patent documentation 3, do not find the content about resistance.
Summary of the invention
A mode of the present invention is optical article (optical element) manufacture method, has following steps:
(a) be formed at the ground floor of other layer of formation light transmission on optical element (forming the step of ground floor); And
(b) at least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, reduces the resistance (falling low-resistance step) of at least a portion on the top layer of ground floor thus,
Describedly fall at least a portion that low-resistance step comprises the top layer that makes described ground floor and become the step of titanium niobium oxide.
In addition, another mode of the present invention is optical article (optical element) manufacture method, has following steps:
(a) be formed at the ground floor of other layer of formation light transmission on optical element (forming the step of ground floor); And
(b) at least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, reduces the resistance (falling low-resistance step) of at least a portion on the top layer of ground floor thus,
Described ground floor is the layer that comprises titanium oxide,
Described the step that low-resistance step comprises ion assisted deposition niobium or niobium oxide falls.
In addition, another mode of the present invention is optical article (optical element) manufacture method, has following steps:
(a) be formed at the ground floor of other layer of formation light transmission on optical element (forming the step of ground floor); And
(b) at least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, reduces the resistance (falling low-resistance step) of at least a portion on the top layer of ground floor thus,
Described ground floor is the oxide skin(coating) of titaniferous and niobium not,
Describedly fall low-resistance step and comprise: after ion assisted deposition titanium or titanium oxide, the step of ion assisted deposition niobium or niobium oxide; Or after ion assisted deposition niobium or niobium oxide, the step of ion assisted deposition titanium or titanium oxide.
The inventor finds, at least one composition of selecting from the group being made up of titanium, niobium, titanium oxide and niobium oxide by ion assisted deposition, even if do not use thus pyroprocessing can reduce the resistance of at least a portion on the top layer of ground floor (film) yet., even if do not use pyroprocessing can utilize titanium-niobium system to give electric conductivity to ground floor yet.Therefore, using the so not high material of the thermotolerances such as glass lens in the optical article of base material, the composition of the ground floor (functional layer) by high refractive index layer for antireflection film etc., charged function and/or the electromagnetic wave shielding function of preventing can be provided, can provide the optical article with above-mentioned functions with low cost.
In addition, in this manufacture method, not only can not use pyroprocessing, and at least one one-tenth of selecting by ion assisted deposition assigns to change the surface (top layer) of ground floor from the group being made up of titanium, niobium, titanium oxide and niobium oxide, can give thus electric conductivity.Therefore, as ITO, can reduce the surperficial resistance of existing layer (ground floor), reach conductive layer to a certain degree without forming thickness.For example, can also reduce the resistance value (resistivity) of the layer (ground floor) that antireflection layer comprises, without the optical design that changes largely the antireflection layer being formed by multilayer.
Falling low-resistance step (above-mentioned (b) step) can think at least a portion on the top layer of ground floor by ion assisted deposition mixed with titanium, niobium and oxygen.In addition, fall low-resistance step (above-mentioned (b) step) and can think that at least a portion on the top layer that makes ground floor becomes titanium niobium oxide and do not use pyroprocessing.
In instructions, become titanium niobium oxide (titanium niobium oxide, TNOization) and be illustrated in doping or mixing niobium atom or niobium oxide in titanium oxide, or, doping or mixed with titanium atom or titanium oxide in niobium oxide, the resistance of observing titanium-niobium oxide system reduces.TNOization at least forms the Ti of anatase titanium dioxide in short-period scope
1-Xnb
xo
2(TNO) crystal or the structure approaching with it, the resistance that result is observed titanium-niobium oxide system reduces.Disclose in the present invention following content: the TNOization that realizes the limited area on top layer by ion assisted deposition, do not use the process (pyroprocessing) that base material is remained on to several Baidu, by resistance be reduced to enough to use the thermotolerances such as eyeglass not the optical article of so high base material give the degree that prevents the function such as charged.
Another advantage of TNOization is that epitaxially grown TNO film is the transparency or approaches transparent.The top layer state of ground floor is because ion assisted deposition changes, and the absorption loss of light may increase.But a kind of composition (crystalline component) likely forming by ion assisted deposition is light transmission, therefore, by the surface of ground floor being carried out to ion assisted deposition, likely can suppresses light transmission and reduce.And the part of improving by ion assisted deposition roughly only limits to the top layer of ground floor.The light transmission that therefore, can further suppress the ground floor causing because of reduction resistance reduces.
Be the layer that comprises titanium oxide at ground floor, fall the step that low-resistance step (step of above-mentioned (b)) comprises ion assisted deposition niobium or its oxide.In addition, be the layer that comprises niobium oxide at ground floor, the step that low-resistance step (step of above-mentioned (b)) comprises ion assisted deposition titanium or its oxide is fallen.And, ground floor as comprise Zirconium oxide layer etc., in the situation of the not oxide (the not oxide skin(coating) of titaniferous and niobium) of titaniferous or niobium, the step of ion assisted deposition niobium or niobium oxide is fallen after low-resistance step (step of above-mentioned (b)) comprises ion assisted deposition titanium or titanium oxide.In addition, the oxide (the not oxide skin(coating) of titaniferous and niobium) that is not titaniferous or niobium at ground floor, the step of ion assisted deposition titanium or titanium oxide is fallen after low-resistance step (step of above-mentioned (b)) comprises ion assisted deposition niobium or niobium oxide.
The exemplary of ground floor is across hard conating or across prime coat and hard conating and the inorganic system of lamination or the antireflection layer of organic system on optical element.In the case of the antireflection layer of inorganic system, ground floor is typically the layer that comprises metal oxide.Ground floor can be any one deck of the antireflection layer of sandwich construction, can be also multiple layers.In which kind of situation, can reduce by application said method the resistance value (resistivity) of antireflection layer.
Like this, ground floor can be the layer that the antireflection layer of sandwich construction comprises.In this case, the method can also further have (c) on ground floor directly or form the step (forming the step of stain-proofing layer) of stain-proofing layers across other layers.Stain-proofing layer has water resistance, and the surface therefore with the optical article of stain-proofing layer can not keep airborne moisture.As a result, easily charged.By application said method, even there is the optical article of stain-proofing layer, also can prevent well charged.
There is the typical case ophthalmic lens in this way of the optical article of stain-proofing layer.In ophthalmic lens, often use glass lens base material as optical element.Said method is applicable to use the situation of glass lens base material as optical element, or optical article is the situation of ophthalmic lens.
The exemplary of optical article, except ophthalmic lens, also can list the information-storing devices such as projection lens, imaging lens, colour splitting prism, cloche, DVD, show ornament that is built-in with medium of good appearance etc.Said method is also applicable to the manufacture of these article.
Brief description of the drawings
Fig. 1 is the cut-open view that the structure of the eyeglass of the antireflection layer of the layer structure of containing type A and Type C is shown.
Fig. 2 is the figure schematically showing for the manufacture of the ion assisted deposition device of antireflection layer.
Fig. 3 gathers the layer material of each layer of the antireflection layer associated with type A and the figure of bed thickness are shown.
Fig. 4 is the cut-open view that the structure of the eyeglass of the antireflection layer of the layer structure of containing type B is shown.
Fig. 5 gathers the layer material of each layer of the antireflection layer associated with type B and the figure of bed thickness are shown.
Fig. 6 gathers the layer material of each layer of the antireflection layer associated with Type C and the figure of bed thickness are shown.
Fig. 7 is the figure that gathers the measurement result that embodiment 1～9 and the surface resistance of comparative example 1 and the absorption loss of light are shown.
Fig. 8 (A) is the cut-open view that the state of measuring surface resistance is shown, Fig. 8 (B) is the vertical view that the state of measuring surface resistance is shown.
Label declaration
1 eyeglass base material (optical element); 2 hard conatings; 3 antireflection layers; 4 stain-proofing layers; 10 eyeglasses (optical article)
Embodiment
Several embodiment of the present invention is described.Below, describe exemplified as the spectacle lens of optical article, but applicable optical article of the present invention is not limited to this.
Fig. 1 illustrates the structure of an example of typical spectacle lens by cut-open view.Eyeglass 10 comprises: eyeglass base material 1; Be formed on the surperficial hard conating 2 of eyeglass base material 1; Be formed on the antireflection layer 3 of the light transmission on hard conating 2; Be formed on the stain-proofing layer 4 on antireflection layer 3.In the present example, use plastic eyeglass base material (glass lens base material) as eyeglass base material 1.As eyeglass base material 1, can also use the eyeglass base material (glass mirror base material) of glass system.
1. eyeglass summary
1.1 eyeglass base materials
Eyeglass base material 1 is not particularly limited, for example can illustrate (methyl) acrylic resin and styrene resin, polycarbonate resin, allyl resin, the allyl carbonate resins such as diethylene glycol bis-allyl carbonate (the such as CR-39 (registered trademark) of PPG イ Application ダ ス ト リ ー ズ オ バ イ オ company), vinyl, vibrin, polyether resin, the urethane resin that makes to react between the hydroxyl compound such as isocyanate compound and diglycol and obtain, thioxanthamide (the チ オ ウ レ タ Application) resin that makes to react between isocyanate compound and multi-thioalcohol compound and obtain, and polymerizable compound that contains (sulfo-) epoxy compound in molecule with more than one disulfide bond etc. is cured and the transparent resin that obtains.The refractive index of eyeglass base material 1 is for example in 1.60～1.75 left and right.In this embodiment, refractive index can, in above-mentioned scope, also can depart from up and down with respect to above-mentioned scope in allowed band.
1.2 hard conatings (prime coat)
Be formed on hard conating 2 on eyeglass base material 1 mainly to improve wear-resisting wiping as object.The material using as hard conating 2, can enumerate acrylic resin, melamine series resin, urethane and be resin, epoxy and be resin, Pioloform, polyvinyl acetal and be resin, amino and be resin, vibrin, polyamide-based resin, vinyl alcohol resin, styrene resin, silicon is resin and their potpourri or co-polymer etc.One example of hard conating 2 is that silicon is resin, be apply comprise metal oxide particle, silane compound coating composition (being used to form the surface coating composition of hard conating) and make it solidify after product.In this coating composition, can comprise the compositions such as (mixing) colloidal silica and multi-functional epoxy compound.
The object lesson of the metal oxide particle that coating composition (being used to form the coating composition of hard conating) comprises is by SiO
2, Al
2o
3, SnO
2, Sb
2o
5, Ta
2o
5, CeO
2, La
2o
3, Fe
2o
3, ZnO, WO
3, ZrO
2, In
2o
3, TiO
2the particle forming Deng metal oxide, or the composite particle being formed by the metal oxide of two or more metals.Also can in coating composition, comprise (mixing) makes these particles be colloidal to be dispersed in the dispersion for example, obtaining in spreading agent (water, alcohol system or other organic solvent).
Hard conating 2 can also be held concurrently and be brought into play the function of prime coat, in order to ensure the adhesion between eyeglass base material 1 and hard conating 2, can also between eyeglass base material 1 and hard conating 2, prime coat be set separately.Prime coat also can effectively improve the impact resistance as the shortcoming of high index of refraction eyeglass base material.As the resin that is used to form prime coat, can enumerate acrylic resin, melamine series resin, urethane and be resin, epoxy and be resin, Pioloform, polyvinyl acetal and be resin, amino and be resin, vibrin, polyamide-based resin, vinyl alcohol resin, styrene resin, silicon is resin and their potpourri or multipolymer etc.As the prime coat for keeping adhesion, preferably urethane is resin and polyester based resin.
The exemplary of the manufacture method of hard conating 2 and prime coat is by infusion process, rotary process, gunite and flow method applying coating composition, afterwards in the method for temperature heat drying a few hours of 40～100 DEG C.
1.3 antireflection layer
The exemplary that is formed on the antireflection layer 3 on hard conating 2 be inorganic be antireflection layer or organic system antireflection layer.Inorganic is that antireflection layer is typically by multilayer film and forms, and for example, the high refractive index layer that the low-index layer that can be 1.3～1.6 by refractive index and refractive index are 1.8～2.6 replaces lamination and forms.The number of plies of this antireflection layer can be for example 5 layers or 7 layers of left and right.As the example of the each layer of inorganics using that forms this antireflection layer, can enumerate SiO
2, SiO, ZrO
2, TiO
2, TiO, Ti
2o
3, Ti
2o
5, Al
2o
3, TaO
2, Ta
2o
5, NdO
2, NbO, Nb
2o
3, NbO
2, Nb
2o
5, CeO
2, MgO, SnO
2, MgF
2, WO
3, HfO
2, Y
2o
3deng.These inorganicss can use separately, or mix two or more uses.As the method that forms antireflection layer, can enumerate dry process, such as vacuum vapour deposition, ion plating method, sputtering method etc.
One of manufacture method of organic system antireflection layer is damp process.For example can be by the utilization method same with hard conating and prime coat, applying coating composition (being used to form the coating composition of antireflection layer), form thus the antireflection layer of organic system, wherein, this coating composition comprises silica-based particle (being also called below " hollow silica is particle ") and the organo-silicon compound with interior void.In coating composition (being used to form the coating composition of antireflection layer), comprise hollow silica and be particle and be because, owing to comprising gas or the solvent that refractive index ratio silicon dioxide is low in interior void, therefore compared with there is no the silica-based particle in cavity, refractive index reduces, thereby can obtain excellent reflection preventing effect.Hollow silica is that particle can utilize method of recording in TOHKEMY 2001-233611 communique etc. to manufacture, and can use mean grain size within the scope of 1～150nm and the hollow silica of refractive index in 1.16～1.39 scopes is particle but be typically.The bed thickness of organic system antireflection layer is the scope of 50～150nm preferably.If blocked up or excessively thin compared with this scope, may can not get enough reflection preventing effects.
In the eyeglass 10 of present embodiment, at least one layer that antireflection layer 3 comprises has the top layer that has reduced resistance.At least one composition of selecting from the group being made up of titanium, niobium, titanium oxide and niobium oxide by ion assisted deposition (using ion beam-assisted method to carry out evaporation), reduces at least resistance on the top layer of one deck (ground floor) thus.
1.4 stain-proofing layer
Often on antireflection layer 3, form waterproof membrane or hydrophilic antifog film (being referred to as anti-soil film) 4.As an example of stain-proofing layer 4, be the surperficial waterproof and oilproof performance that improves eyeglass 10 be object, be formed on the layer that the organo-silicon compound by fluorine-containing on antireflection layer 3 form.As fluorine-containing organo-silicon compound, preferably use the fluorine containing silane compound of recording in for example TOHKEMY 2005-301208 communique and TOHKEMY 2006-126782 communique.
Fluorine containing silane compound is preferably used as and is dissolved in the water-proofing treatment liquid (being used to form the coating composition of stain-proofing layer) that is adjusted to normal concentration in organic solvent.For example, can form stain-proofing layer 4 by apply this water-proofing treatment liquid on antireflection layer 3.As painting method, can use infusion process, spin-coating method etc.In addition, can also in metallic particles (pellet), fill after water-proofing treatment liquid and form stain-proofing layer 4 by dry processes such as vacuum vapour depositions.
Though the bed thickness of the stain-proofing layer 4 that comprises fluorine containing silane compound is not particularly limited, preferably 0.001～0.5 μ m.More preferably 0.001～0.03 μ m.If the bed thickness of stain-proofing layer 4 is too thin, waterproof oil-proof result is inadequate, if too thick, surfaces of tacky, therefore not preferred.In addition,, if the thickness of stain-proofing layer 4 exceedes 0.03 μ m, may reduce reflection preventing effect.
2. sample manufacture
2.1 embodiment 1 (layer structure: type A)
2.1.1 the selection of eyeglass base material and the formation of hard conating
As eyeglass base material 1, use the eyes glass lens base materials (trade name: セ イ コ ー ス ー パ ー ソ Block リ Application (SSV) (Seiko Epson (Co., Ltd.) manufacture)) of refractive index 1.67.
Modulate in such a way the coating liquid (being used to form the coating solution of hard conating) that is used to form hard conating 2.In epoxy resin-silica mixture (trade name: the acid anhydrides that mixes 4.46 weight portions in コ Application プ セ ラ Application E102 (waste river chemical industry (Co., Ltd.) manufacture) is that hardening agent (trade name: hardening agent liquid (C2) (waste river chemical industry (Co., Ltd.) manufacture)) stirs, and obtains coating liquid of 20 weight portions.Use rotary coating machine on eyeglass base material 1, to apply this coating liquid to specific thickness, form thus hard conating 2.With 125 DEG C to eyeglass base material 1 (having formed the eyeglass base material 1 after the hard conating 2) roasting 2 hours after coating.Thus, on eyeglass base material 1, form the hard conating 2 that bed thickness is about 2 μ m.Below, the product that is formed with bed thickness and is about the hard conating 2 of 2 μ m on eyeglass base material 1 is called to eyeglass sample 10a.
2.1.2 the formation of antireflection layer
2.1.2.1 evaporation coating device
Next, utilize the evaporation coating device 100 shown in Fig. 2 on eyeglass sample 10a, to form the antireflection layer 3 of inorganic system.The illustrative evaporation coating device 100 of Fig. 2 is electron beam evaporation plating devices, has vacuum tank 110, exhaust apparatus 120 and gas supply device 130.Vacuum tank 110 has: sample holder 114, and its placement is formed with the eyeglass sample 10a of hard conating 2; Well heater 115 for base material heating, it is for heating the eyeglass sample 10a being placed in sample holder 114; And filament 116, it produces thermoelectron.This evaporation coating device 100 utilizes electron gun (not shown) to make its evaporation to the deposition material irradiation thermoelectron being placed on evaporation source (crucible) 112 and 113, makes deposition material evaporation to eyeglass sample 10a.
And this evaporation coating device 100 possesses ion gun 117 for energy ion assisted deposition, this ion gun 117 makes import to the gas ionization of ion gun inside and accelerate, and is irradiated to eyeglass sample 10a.In following example, use argon gas is auxiliary for ion after argon ion is accelerated, and as the gas importing, is not limited to argon (Ar), can use oxygen (O
2), nitrogen (N
2), helium (He), neon (Ne), xenon (Xe) etc.
The turbomolecular pump comprising by exhaust apparatus 120 or cryopump 121 and pressure-regulating valve 122, the inside of vacuum tank 110 remains on high vacuum for example 1 × 10
-4under Pa.On the other hand, the inside of vacuum tank 110 also can be by gas supply device 130 in regulation gas atmosphere.For example, in gas container 131, prepare argon (Ar), nitrogen (N
2), oxygen (O
2) etc.The flow of gas can be controlled by volume control device 132, the interior pressure of vacuum tank 110 can be controlled by pressure gauge 135.In addition, in vacuum tank 110, can also be provided for removing the cold-trap of residual moisture and for managing the device etc. of bed thickness of the layer that will form.The device of bed thickness of the layer that will form as management, for example, have blooming meter and the quartz vibrator film thickness gauge etc. of reflection-type.Base material heating is for example infrared lamp with well heater 115, and by heating eyeglass sample, 10a emits gas or splashes moisture, guarantees the adhesion of the layer that is formed on eyeglass sample 10a surface.
The main evaporation condition of this evaporation coating device 100 be deposition material, electron gun accelerating potential, current value, have or not ion auxiliary.Magnitude of voltage by ionic species (atmosphere of vacuum tank 110), ion gun 117 and current value provide the condition while utilizing ion auxiliary.Hereinafter, unless there is special record, the accelerating potential of electron gun is in the scope of 5～10kV, and current value, in the scope of 50～500mA, forms speed (film forming speed) according to layer and selects.In addition, in the situation that utilizing ion auxiliary, the magnitude of voltage of electron gun 117 is in the scope of 200V～1kV, and current value, in the scope of 100～500mA, is selected according to layer formation speed (film forming speed) etc.
2.1.2.2 the film forming of low-index layer and high refractive index layer
First, utilize acetone to clean the eyeglass sample 10a that is formed with hard conating 2, carry out the heat treated of approximately 70 DEG C in the inside of vacuum tank 110, make to be attached to the moisture evaporation on eyeglass sample 10a.Then, Ion Cleaning is implemented in the surface of eyeglass sample 10a.Particularly, use ion gun 117 with the energy of hundreds of electron-volt the surface irradiation oxygen ion beam to eyeglass sample 10a, remove the organism that is attached to eyeglass sample 10a surface.By the method, can strengthen the adhesion of the layer that is formed on eyeglass sample 10a surface.In addition, also can use for example argon gas of inert gas (Ar), xenon (Xe), nitrogen (N
2) etc. replace oxonium ion and carry out same processing, or also can irradiate oxygen radical or oxygen plasma.
After the abundant vacuum exhaust in the inside of vacuum tank 110, by electron beam vacuum vapour deposition alternately lamination as the silicon dioxide (SiO of low-index layer 31
2) layer, as the titanium dioxide (TiO of high refractive index layer 32
2) layer, form antireflection layer 3.
The layer structure of the antireflection layer 3 of this example (type A) is 7 layers of structure (with reference to Fig. 1), and the 1st layer, the 3rd layer, the 5th layer and the 7th layer is that 31, the 2 layers of low-index layers, the 4th layer, the 6th layer are high refractive index layers 32.Low-index layer 31 is SiO
2layer, by vacuum evaporation silicon dioxide (SiO
2) and do not carry out ion and assist to form (film forming).Film forming speed is that the accelerating potential of 2.0nm/sec, electron gun is that 7kV, electric current are 100mA.
High refractive index layer 32 is TiO
2layer.By importing oxygen while ion assisted deposition titanium dioxide (TiO
2) form (film forming).Film forming speed is 0.4nm/sec, and the accelerating potential of electron gun is 7kV, and electric current is 360mA.The bed thickness of the 1st layer～the 7th layer is managed respectively as 28nm, 6.6nm, 204nm, 23nm, 36nm, 28nm, 100nm.Below, by this TiO
2/ SiO
27 layers of structure of system are called type A.In Fig. 3, gather the layer material of each layer and the bed thickness (nm) that show type A.In addition, in this eyeglass sample 10a, the refractive index of hard conating 2 is 1.65, SiO
2the refractive index of layer 31 is 1.462, TiO
2the refractive index of layer 32 is 2.43.
2.1.2.3 reduce resistance
In this embodiment 1, amass layer by layer the 6th layer from the 1st, in the following way the top layer 33 of the 6th layer is changed to (reduction resistance).In addition, having reduced after the resistance on top layer of the 6th layer, form (film forming) the 7th layer.
At the TiO having formed as the 6th layer
2after layer 32, make auxiliary (ion beam-assisted) method of ion of argon gas ionic discharge, make niobium oxide (Nb
2o
5) pile up under the condition of about 2nm and carry out evaporation.The condition of ion beam-assisted is as described below.
Vapor deposition source: niobium oxide (Nb
2o
5)
Assist gas: argon (Ar)
Accelerating potential: 1000V, acceleration electric current: 200mA
2.1.3 the formation of stain-proofing layer
Forming after antireflection layer 3, then form stain-proofing layer 4.Oxygen plasma treatment is implemented on the surface of the 7th layer at antireflection layer 3, at interior (film forming) stain-proofing layer 4 that forms particulate material as vapor deposition source of evaporation coating device 100, this particulate material comprises " KY-130 " (trade name, SHIN-ETSU HANTOTAI's chemical industry (Co., Ltd.) are manufactured) of containing the fluorine-containing organic silicon compound that molecular weight is larger.Now, with about 500 DEG C of heating, make KY-130 evaporation.The evaporation time is about about 3 minutes.Owing to passing through to implement oxygen plasma treatment, at the SiO of final layer (the 7th layer)
2the surface of layer 31 forms silanol group, has therefore improved the chemical adhesion (chemical bond) between antireflection layer 3 and stain-proofing layer 4.
Be through with after evaporation, take out from vacuum deposition apparatus 100 the eyeglass sample 10a that is formed with antireflection layer 3 and stain-proofing layer 4 at a face, after reversion, again drop into, with identical reiteration above-mentioned steps (formation of antireflection layer 3 and stain-proofing layer 4).Thus, also form antireflection layer 3 and stain-proofing layer 4 at another face, produce satisfied eyeglass 10.Take out from vacuum deposition apparatus 100 eyeglass 10 producing.
Antireflection layer 3 and the stain-proofing layer 4 of layer (the 1st layer) (particularly, having reduced the resistance on the top layer of the 6th layer) of the resistance that the eyeglass 10 of embodiment 1 has hard conating 2 on the two sides of glass lens base material 1, comprise a part that has at least reduced top layer.
2.2 embodiment 2 (layer structure: type B)
The structure of the spectacle lens of embodiment 2 is shown by cut-open view in Fig. 4.Be of five storeys 3, the 1 layers, the 3rd layer and the 5th layer of the antireflection layer of structure of eyeglass 10 tools of this example (type B) is that 31, the 2 layers of low-index layers and the 4th layer are high refractive index layers 32.
The manufacture method of this routine eyeglass 10 is with respect to embodiment 1, and difference is above-mentioned 2.1.2.2 (film forming of low-index layer and high refractive index layer) and above-mentioned 2.1.2.3 (reduction resistance).Other step is identical with embodiment 1.
Low-index layer 31 is SiO
2layer, identical with the low-index layer 31 of embodiment 1, be by vacuum evaporation silicon dioxide (SiO
2) and do not carry out auxiliary form (film forming) of ion.High refractive index layer 32 is Nb
2o
5layer, identical with the high refractive index layer 32 of embodiment 1, be by importing oxygen while ion assisted deposition niobium oxide (Nb
2o
5) formation (film forming).The bed thickness of the 1st layer～the 5th layer is managed into respectively 36nm, 37nm, 15.8nm, 65.3nm, 91nm.Below, by this Nb
2o
5/ SiO
25 layers of structure of system are called type B.In Fig. 5, gather the layer material of each layer and the bed thickness (nm) that show type B.
In this embodiment 2, amass layer by layer after the 4th layer from the 1st, as follows the top layer 33 of the 4th layer is changed to (reduction resistance).In addition, the 5th layer is to form (film forming) after having reduced the resistance on top layer of the 4th layer.
At the Nb having formed as the 4th layer
2o
5after layer 32, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
x(X=1.7)) pile up under the condition of about 2nm and carry out evaporation.Next, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.Ion beam-assisted condition is as follows respectively.
Vapor deposition source: titanium dioxide (TiO
x(X=1.7)), niobium oxide (Nb
2o
5)
Assist gas: argon (Ar)
Accelerating potential: 1000V, acceleration electric current: 200mA
2.3 embodiment 3 (layer structure: type A)
3, the 1 layers, the 3rd layer, the 5th layer and the 7th layer of the antireflection layer that this routine eyeglass 10 has 7 layers of structure is as shown in figures 1 and 3 that 31, the 2 layers of low-index layers, the 4th layer and the 6th layer are high refractive index layers 32.The manufacture method of this routine eyeglass 10 is with respect to embodiment 1, above-mentioned 2.1.2.3 (reduction resistance) difference, and other step is identical with embodiment 1.
In this embodiment 3, amass layer by layer after the 6th layer from the 1st, as follows the top layer 33 of the 6th layer is changed to (reduction resistance).In addition, the 7th layer is to form (film forming) after having reduced the resistance on top layer of the 6th layer.
At the TiO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.The condition of ion beam-assisted is as follows.
Vapor deposition source: niobium oxide (Nb
2o
5)
Assist gas: argon (Ar)
Accelerating potential: 1000V, acceleration electric current: 200mA
2.4 embodiment 4 (layer structure: type A)
This routine eyeglass 10 is identical with embodiment 3, has the layer structure (TiO of type A
2/ SiO
2system 7 layers of structure) antireflection layer 3.The manufacture method of this routine eyeglass 10 is with respect to embodiment 3, and difference is above-mentioned 2.1.2.3 (reduction resistance).
In this example, reduce as follows resistance.At the TiO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 2nm and carry out evaporation.Then, use ion evaporation (ion beam-assisted) method making titanium dioxide (TiO
x(X=1.7)) pile up under the condition of about 1mm and carry out evaporation.The condition of ion beam-assisted is as follows respectively.
Vapor deposition source: niobium oxide (Nb
2o
5), titanium dioxide (TiO
x(X=1.7))
Assist gas: argon (Ar)
Accelerating potential: 1000V, acceleration electric current: 200mA
2.5 embodiment 5 (layer structure: Type C)
This routine eyeglass 10 has the antireflection layer 3 of 7 layers of structure shown in Fig. 1.The 1st layer, the 3rd layer, the 5th layer and the 7th layer is that 31, the 2 layers of low-index layers, the 4th layer and the 6th layer are high refractive index layers 32.Wherein, low-index layer 31 is SiO
2, high refractive index layer 32 is ZrO
2layer (refractive index 2.1).
The manufacture method of this routine eyeglass 10 is with respect to embodiment 1, and difference is above-mentioned 2.1.2.2 (film forming of low-index layer and high refractive index layer) and above-mentioned 2.1.2.3 (reduction resistance).Other step is identical with embodiment 1.
Low-index layer 31 is SiO
2layer, identical with the low-index layer 31 of embodiment 1, be by vacuum evaporation silicon dioxide (SiO
2) and do not carry out auxiliary form (film forming) of ion.High refractive index layer 32 is ZrO
2layer is by using ZrO sintered body to import oxygen while ion assisted deposition zirconia (ZrO
2) formation (film forming).Film forming speed is 0.8nm/sec, and the accelerating potential of electron gun is 7kV, and electric current is 280mA.The bed thickness of the 1st layer～the 7th layer is managed into respectively 24nm, 8.5nm, 191nm, 39nm, 15nm, 56nm, 91nm.Below, by this ZrO
2/ SiO
27 layers of structure of system are called Type C.In Fig. 6, gather the layer material of each layer and the bed thickness (nm) that show Type C.
In addition, in this embodiment 5, amass layer by layer after the 6th layer from the 1st, as follows the top layer 33 of the 6th layer is changed to (reduction resistance).In addition, the 7th layer is that the resistance that has reduced the top layer of the 6th layer forms (film forming) afterwards.
(reduction resistance)
At the ZrO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
2) pile up under the condition of about 2nm and carry out evaporation.Next, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.And, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
2) pile up under the condition of about 2nm and carry out evaporation.And, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.The condition of ion beam-assisted is as follows respectively.
Vapor deposition source: titanium dioxide (TiO
2), niobium oxide (Nb
2o
5), titanium dioxide (TiO
2),
Niobium oxide (Nb
2o
5)
Assist gas: argon (Ar)
Accelerating potential: 800V, acceleration electric current: 200mA
2.6 embodiment 6 (layer structure: Type C)
Utilize above-mentioned 2.1.2.3 (reduction resistance) and method that other step with embodiment 5 identical different from embodiment 5, manufacture the eyeglass 10 of the layer structure with the Type C identical with embodiment 5.
Above-mentioned 2.1.2.3 (reduction resistance) carries out as follows.At the ZrO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.Then, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
x(X=1.7)) pile up under the condition of about 2nm and carry out evaporation.And, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.The condition of ion beam-assisted is as follows respectively.
Vapor deposition source: niobium oxide (Nb
2o
5), titanium dioxide (TiO
x(X=1.7)), niobium oxide (Nb
2o
5)
Assist gas: argon (Ar)
Accelerating potential: 800V, acceleration electric current: 200mA
2.7 embodiment 7 (layer structure: Type C)
Utilize above-mentioned 2.1.2.3 (reduction resistance) and method that other step with embodiment 5 identical different from embodiment 5, manufacture the eyeglass 10 of the layer structure with the Type C identical with embodiment 5.
Above-mentioned 2.1.2.3 (reduction resistance) carries out as follows.At the ZrO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
2) pile up under the condition of about 2nm and carry out evaporation.Then, use auxiliary (ion beam-assisted) method of ion making niobium oxide (Nb
2o
5) pile up under the condition of about 1nm and carry out evaporation.And, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
2) pile up under the condition of about 2nm and carry out evaporation.The condition of ion beam-assisted is as follows respectively.
Vapor deposition source: titanium dioxide (TiO
2), niobium oxide (Nb
2o
5), titanium dioxide (TiO
2)
Assist gas: argon (Ar)
Accelerating potential: 800V, acceleration electric current: 200mA
2.8 embodiment 8 (layer structure: Type C)
Utilize above-mentioned 2.1.2.3 (reduction resistance) and method that other step with embodiment 5 identical different from embodiment 5, manufacture the eyeglass 10 of the layer structure with the Type C identical with embodiment 5.
Above-mentioned 2.1.2.3 (reduction resistance) carries out as follows.At the ZrO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion to carry out evaporation metal niobium (Nb) is piled up under the condition of about 2nm.Then, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
x(X=1.7)) pile up under the condition of about 3nm and carry out evaporation.And, use auxiliary (ion beam-assisted) method of ion to carry out evaporation metal niobium (Nb) is piled up under the condition of about 1nm.The condition of ion beam-assisted is as follows respectively.
Vapor deposition source: metal niobium (Nb), titanium dioxide (TiO
x(X=1.7)), metal niobium (Nb)
Assist gas: argon (Ar)
Accelerating potential: 1000V, acceleration electric current: 200mA
2.9 embodiment 9 (layer structure: Type C)
Utilize above-mentioned 2.1.2.3 (reduction resistance) and method that other step with embodiment 5 identical different from embodiment 5, manufacture the eyeglass 10 of the layer structure with the Type C identical with embodiment 5.
Above-mentioned 2.1.2.3 (reduction resistance) carries out as follows.At the ZrO having formed as the 6th layer
2after layer 32, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
x(X=1.7)) pile up under the condition of about 2nm and carry out evaporation.Then, use auxiliary (ion beam-assisted) method of ion to carry out evaporation metal niobium (Nb) is piled up under the condition of about 1nm.And, use auxiliary (ion beam-assisted) method of ion making titanium dioxide (TiO
x(X=1.7)) pile up under the condition of about 2nm and carry out evaporation.The condition of ion beam-assisted is as follows respectively.
Vapor deposition source: titanium dioxide (TiO
x(X=1.7)), metal niobium (Nb), titanium dioxide (TiO
x(X=1.7))
Assist gas: argon (Ar)
Accelerating potential: 1000V, acceleration electric current: 200mA
2.10 comparative example 1
As a comparative example 1, utilize to omit and fall low-resistance step, the method that other step is identical with embodiment 5, manufacture has the eyeglass 10 of the layer structure of the Type C identical with embodiment 5.
3. the evaluation of the eyeglass sample producing by embodiment 1～9 and comparative example 1
For the eyeglass sample producing by above-described embodiment 1～9 and comparative example 1, measure the absorption loss of resistance and light.These measurement results (evaluation result) gather and illustrate in Fig. 7.
3.1 resistance
3.1.1 determinator and assay method
At Fig. 8 (A) with the situation of the surperficial resistance (surface resistance) of measuring each sample has been shown (B).In this example, making ring-shaped probe 61 contact measurement objects is the surperficial 10F of eyeglass sample 10, measures the resistance value of the surperficial 10F of eyeglass sample 10.The height opposing opposing rate Meter Ha イ レ ス タ UP MCP-HT450 type that determinator 60 uses Mitsubishi Chemical (Co., Ltd.) to manufacture.The ring-shaped probe 61 using is URS types, has two electrodes.The external diameter of exterior annular electrode 61a is 18mm, and internal diameter is 10mm, and the diameter of inner circular electrode 61b is 7mm.Between these electrodes, apply the voltage of 1000V～10V, the sheet resistance value of the each sample of instrumentation.
3.1.2 evaluation result
As shown in Figure 7, in the eyeglass sample that utilizes the method for comparative example 1 to form, the measured value of surface resistance is 1 × 10
13Ω.In the eyeglass sample that the method for utilizing embodiment 1～9 to record in order to reduce resistance forms, the measured value of surface resistance is reduced to 2 × 10
8Ω～8 × 10
9Ω.That is, known and existing sample comparison, the resistance value that the method for utilizing embodiment 1～9 to record has reduced the eyeglass sample of resistance reduces 4～5 (10
4～10
5) left and right.Resistance value can be 1/10
4～1/10
5.Therefore, known on the top layer of a layer that forms antireflection layer, at least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, can reduce surface resistance thus.
In these embodiment 1～9, at least one composition of selecting from the group being made up of titanium, niobium, titanium oxide and niobium oxide by ion assisted deposition is sneaked into titanium (Ti) atom, niobium (Nb) atom, oxygen (O) atom thus on top layer 33.For example, in embodiment 1 and 2, ion assisted deposition niobium oxide or metal niobium and even titanium oxide on the top layer 33 of the titanium oxide layer as the 6th layer of ground floor or the 4th layer, thus, the niobium of can thinking to adulterate in the top layer (skin section) 33 in titanium oxide layer, can think to form Ti-Nb-O layer or region at least a portion on top layer 33.And because the resistance on surface in above-mentioned evaluation result is minimized, therefore, in the Ti-Nb-O layer forming by ion assisted deposition or region, at least a portion of titanium becomes anatase titanium dioxide crystal or approaches the state of anatase titanium dioxide crystal, can think by TNOization.Therefore, keep base material without the high temperature with more than 300 degree, can be on the top layer 33 of titanium oxide layer or the part on top layer 33 of the 6th layer or the 4th layer, form Ti-Nb-O layer or region by ion assisted deposition, thus, can think at least to have formed TNO or the crystal state approaching with it in short-period scope.Therefore, be not suitable for the base material of pyroprocessing, for example, in the glass lens base material of this example, also can importing TNO at the borderline region on layer surface, can realize and reduce resistance by TNO.
In addition, this Ti-Nb-O layer or region are to form by the such method of ion assisted deposition Titanium, titanium oxide, metal niobium or niobium oxide on top layer 33, are different from the high refractive index layer that comes the titanium that lamination titanium-niobium potpourri forms-niobium system by evaporation.That is, the in the situation that of evaporation titanium-niobium potpourri, only however evaporation in high-temperature substrates and epitaxial growth just can not reduce resistance.Therefore for the existing high refractive index layer of titanium-niobium system, low-resistance report is not fallen.In the above embodiments 1 and 2, it not the potpourri of evaporation titanium-niobium, but a side of titanium or niobium is carried out to ion assisted deposition with respect to the opposing party's oxide, top layer 33 or its a part of titanium become anatase titanium dioxide thus, can think to have formed the TNO of electric conductivity.
Equally, in embodiment 3 and 4, on the top layer 33 of the niobium oxide layer of the 6th layer as ground floor, ion assisted deposition titanium oxide or Titanium and even niobium oxide, thus, can think the titanium that adulterated in the top layer of niobium oxide layer (skin section) 33, can think to have formed Ti-Nb-O layer or region at least a portion on top layer 33.As shown in embodiment 5～9, on the top layer 33 of the Zirconium oxide layer of the 6th layer as ground floor, ion assisted deposition titanium oxide or Titanium, niobium oxide or metal niobium, thus, can think to have formed Ti-Nb-O layer or region at least a portion on the top layer of Zirconium oxide layer (skin section) 33.And resistance is also minimized in these embodiments, can think not use pyroprocessing can make at least a portion TNOization on top layer 33.
By reducing the surface resistance of the optical articles such as eyeglass, cloche, can obtain several effects.Typical effect is to prevent charged and shielding electromagnetism.In spectacle lens, have or not the standard of charged preventive can think that resistance value is 1 × 10
11below Ω.In the time considering security in use etc., more preferably resistance value is 1 × 10
10below Ω.In the eyeglass sample that the method for recording by embodiment 1～embodiment 9 produces, it is 1 × 10 that any one eyeglass sample all has resistance value
10excellent charged preventive below Ω.In these embodiments, only process the top layer of a layer of the antireflection film of sandwich construction, just determined enough resistance and reduced, can increase hardly man-hour and reduce resistance.Certainly, also can process the top layer of multiple layers of the antireflection film of sandwich construction.
In addition, in the processing of top layer ion assisted deposition titanium, titanium oxide, niobium, niobium oxide, with high refractive index layer in order to form antireflection film and the processing of evaporation titanium oxide and niobium oxide is compared, something in common is more, therefore, almost can directly be suitable for the processing that forms antireflection film.In this, be the processing that can easily be used as the surface resistance that reduces the optical articles such as eyeglass in the processing of top layer ion assisted deposition titanium, titanium oxide, niobium, niobium oxide.
3.2 absorption loss
3.2.1 determinator and assay method
Next, measure the absorption loss of the light of each eyeglass sample.But if surface curvature, the absorption loss of light is difficult to measure.Therefore, use the base material (glass baseplate) 1 of glass manufacture, utilize the step same with eyeglass sample manufacture each embodiment for measuring the sample (glass sample) of optical absorption loss, measure absorption loss with glass sample.
The absorption loss of light is measured reflectivity and transmissivity with spectrophotometer, and (A) formula of utilization is calculated absorptivity.The spectrophotometer U-4100 that uses Hitachi to manufacture in mensuration.
Absorptivity (absorption loss)=100%-transmissivity-reflectivity (A)
The measurement result of the average light absorptivity of the wavelength 400～700nm of each glass sample has been shown in Fig. 7.
3.2.2 evaluation result
Can see, with respect to the glass sample of comparative example 1, the absorption loss of the glass sample producing by embodiment 1～embodiment 9 more or less increases.But maximum is also below 2%, light transmission is fully high, and the increase of optical absorption loss can not reach the degree of the light transmission of antireflection layer 3 being brought to considerable influence.Therefore, can be judged as the eyeglass sample that the method recorded by embodiment 1～embodiment 9 forms and there is enough light transmissions as spectacle lens.
On the top layer 33 of a layer that forms antireflection layer, at least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, the optical states on top layer 33 is upset thus, and optical absorption loss increases.On the other hand, in the present example, can think to form TNO in the part on top layer 33, TNO itself is the layer of transparent electric conductivity.Therefore, the absorption loss of known light less increases, and can reduce surperficial resistance and can bring impact to the optical property of optical article hardly.
3.3 comprehensive evaluation
Known by above each evaluation, the eyeglass sample that the method for recording by embodiment 1～embodiment 9 forms, be the optical article that surface resistance is reduced to degree enough with regard to preventing the objects such as charged and shielding electromagnetic wave, and optical property does not almost reduce.These eyeglass samples are because the cost of titanium and niobium is compared with the low and less problem that has resource exhaustion etc., and can realize reduction resistance with the lower material of toxicity, with respect to the eyeglass sample that uses ITO (it comprises costliness and can say the indium that resource is not enriched), industrially advantage is more.
And, in manufacture method provided by the invention, in the temperature that substantially does not need to improve base material aspect reduction resistance, be the above pyroprocessing of such 300 degree of transparency electrode without manufacturing titanium-niobium.Therefore, the present invention is applicable to the optical article that glass lens etc. comprises the base material that high temperature durability is lower.
In addition, reduce as mentioned above the resistance on the top layer of ground floor, but be not limited to this layer, even on this layer overlapping several layers, surperficial resistance value or resistivity also can be reduced.Therefore, fall low-resistance layer of the 4th layer or the 6th layer of 7 layers of structure that is not limited to 5 layers of structure, can be any one deck, and then also can reduce the resistance on the top layer of multiple layers.
In addition, the layer structure of the antireflection layer shown in above-described embodiment is only several examples, the invention is not restricted to these layer of structure.For example, also or 9 layer above antireflection layer following applicable to 3 layers, in this situation, fall low-resistance layer and are not limited to one deck.In addition, the combination of high refractive index layer and low-index layer is not limited to TiO
2/ SiO
2, Nb
2o
5/ SiO
2, ZrO
2/ SiO
2, can be also Ta
2o
5/ SiO
2, NdO
2/ SiO
2, HfO
2/ SiO
2, AL
2o
3/ SiO
2deng.Even these systems, the resistance on the top layer by any one deck of reduction described above, thus, also can reduce the resistance value of antireflection layer 3, improves electric conductivity.
The manufacture method of optical article of the present invention is not limited to spectacle lens, also applicable to information-storing devices such as projection lens, imaging lens, colour splitting prism, cloche, DVD, show ornament that is built-in with medium of good appearance etc., can provide and there is the charged optical article that prevents function.In addition, the embodiment shown in above-mentioned is only illustrating, and those skilled in the art can utilize the manufacture method of the optical article that the present invention obtains to be also contained in the present invention.
Claims (15)
1. an optical article manufacture method, wherein, this optical article manufacture method has following steps:
At the ground floor that is formed at other layer of formation light transmission on optical element; And
At least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, reduces the resistance of at least a portion on the top layer of described ground floor thus,
Describedly fall at least a portion that low-resistance step comprises the top layer that makes described ground floor and become the step of titanium niobium oxide.
2. optical article manufacture method according to claim 1, wherein,
Described ground floor is the layer that the antireflection layer of sandwich construction comprises.
3. optical article manufacture method according to claim 2, wherein,
This optical article manufacture method also has on described ground floor directly or across the step of other layer of formation stain-proofing layer.
4. optical article manufacture method according to claim 1, wherein,
Described optical element is glass lens base material.
5. optical article manufacture method according to claim 4, wherein,
This optical article is eyeglass.
6. an optical article manufacture method, wherein, this optical article manufacture method has following steps:
At the ground floor that is formed at other layer of formation light transmission on optical element; And
At least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, reduces the resistance of at least a portion on the top layer of described ground floor thus,
Described ground floor is the layer that comprises titanium oxide,
Described the step that low-resistance step comprises ion assisted deposition niobium or niobium oxide falls.
7. optical article manufacture method according to claim 6, wherein,
Described ground floor is the layer that the antireflection layer of sandwich construction comprises.
8. optical article manufacture method according to claim 7, wherein,
This optical article manufacture method also has on described ground floor directly or across the step of other layer of formation stain-proofing layer.
9. optical article manufacture method according to claim 6, wherein,
Described optical element is glass lens base material.
10. optical article manufacture method according to claim 9, wherein,
This optical article is eyeglass.
11. 1 kinds of optical article manufacture methods, wherein, this optical article manufacture method has following steps:
At the ground floor that is formed at other layer of formation light transmission on optical element; And
At least one composition that ion assisted deposition is selected from the group being made up of titanium, niobium, titanium oxide and niobium oxide, reduces the resistance of at least a portion on the top layer of described ground floor thus,
Described ground floor is the oxide skin(coating) of titaniferous and niobium not,
Describedly fall low-resistance step and comprise: after ion assisted deposition titanium or titanium oxide, the step of ion assisted deposition niobium or niobium oxide; Or after ion assisted deposition niobium or niobium oxide, the step of ion assisted deposition titanium or titanium oxide.
12. optical article manufacture methods according to claim 11, wherein,
Described ground floor is the layer that the antireflection layer of sandwich construction comprises.
13. optical article manufacture methods according to claim 12, wherein,
This optical article manufacture method also has on described ground floor directly or across the step of other layer of formation stain-proofing layer.
14. optical article manufacture methods according to claim 11, wherein,
Described optical element is glass lens base material.
15. optical article manufacture methods according to claim 14, wherein,
This optical article is eyeglass.
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| JP2009185495A JP5588135B2 (en) | 2009-08-10 | 2009-08-10 | Method for manufacturing optical article |
| JP2009-185495 | 2009-08-10 |
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| US (1) | US20110033635A1 (en) |
| EP (1) | EP2286985B1 (en) |
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| JP2011013654A (en) * | 2008-10-23 | 2011-01-20 | Seiko Epson Corp | Multilayer antireflection layer and method of producing the same, and plastic lens |
| JP2010231171A (en) * | 2009-03-04 | 2010-10-14 | Seiko Epson Corp | Optical article and method for producing the same |
| JP5523066B2 (en) * | 2009-11-17 | 2014-06-18 | ホーヤ レンズ マニュファクチャリング フィリピン インク | Method for manufacturing optical article |
| JP2012032690A (en) | 2010-08-02 | 2012-02-16 | Seiko Epson Corp | Optical article and manufacturing method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5588135B2 (en) | 2014-09-10 |
| JP2011039218A (en) | 2011-02-24 |
| EP2286985B1 (en) | 2015-10-14 |
| EP2286985A1 (en) | 2011-02-23 |
| CN101995588A (en) | 2011-03-30 |
| US20110033635A1 (en) | 2011-02-10 |
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